Certain phosphorodithiolates as insecticides and fungicides

ABSTRACT

Method for controlling insects and fungi, in which the insects and fungi are contacted with a phosphorodithiolate of the formula,   WHEREIN R is a lower alkyl; A is a lower alkyl, etc.; and B is phenylalkyl, etc. Two typical examples of the phosphorodithiolates are shown by the formula   The compounds can be prepared by condensing a dithioate of the formula,   WHEREIN A and R are as mentioned above and M is an alkali metal or ammonium group, with a halide of the formula,

O United States Patent 11 1 1111 3,725,546

Tsuchiya et al. 1 51 Apr. 3, 1973 CERTAIN PHOSPHORODITHIOLATES ABSTRACT AS INSECTICIDES AND FUNGICIDES Method for controlling insects and fungi, in which the [75] Inventors: Hiroshi Tsuchiya, Ashiya; Kunio insects i fungi are contacted with a Mukai, NishinomiyaxAkio Kimum phosphorodlthlolate of the formula, Takarazuka; Keimei Fujimoto, n Kyoto; Toshiaki Ozaki; Sigeo g Yamamoto, both of Toyonaka; I Yositosi Okuno, Nishinomiya; Taizo 0R Ogawa, Minoo; Toshiyuki Wakatsuki Kyoto; Yoshihiko Nishizawa, wherelrl R 1s a lower alkyl; A 15 a lower alkyl, etc.; and Nara allot-Japan B is phenylalkyl, etc. Two typical examples of the phosphorodithiolates are shown by the formula [73] Assignee: Sumitomo Chemical Company, Ltd.,

Osaka, Japan 0 [22] Flled: Aug. 5, 1970 II sflpnk [21] Appl. No.2 61,468 (3111119 Related U.S. Application Data [63] Continuation-in-part of Ser. No. 690,725, Dec. 15, cmsplrmsmcnk 1967, abandoned. 0 01115 [52] U.S. Cl. ..424/225, 424/218, 4422412212911, The compounds can be p p y condensing a 51 1m. 01. ..A0ln 9/36 dthmte fmmula [58] Field of Search ..424/2l8, 224, 225, 219 o A-S-P 111 [56] References Clted S UNITED STATES PATENTS wherein A and R are as mentioned above and M is an 3,641,221 2/1972 Schraderet al. ...........,.........260 949 alkali metal or ammonium roup, with a halide of the formula, FOREIGN PATENTS OR APPLICATIONS 938,850 10/1963 Great Britain.........., ..........424[Z24 B Hal Primary Examiner-Albert T. Meyers Assistant Examiner-Vincent D. Turner Attorney-Stevens, Davis, Miller & Mosher wherein B is as mentioned above and Hal is a halogen.

6 Claims, No Drawings CERTAIN PHOSPHORODITHIOLATES AS INSECTICIDES AND FUNGICIDES doned.

The present invention relates to a novel use of phosphorodithiolates of the formula,

AS i SB OR wherein R is a C C alkyl group, A is an alkyl group, a cycloalkyl group or a phenylalkyl group of the formuwherein D is an alkylene group, X is a hydrogen atom, a halogen atom, an alkyl group or a nitro group and n is an integer of 1 to S, and B is an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group or a phenylalkyl group of the formula,

wherein D is an alkylene group and X and n have same meanings as defined above, provided that B is a phenylalkyl group when A is an alkyl group and that the total number of the carbon atoms of the alkylene groups of D and D is 3 or more when both A and B are the phenylalkyl groups.

At present, the application as agricultural chemicals of organo-mercuric compounds, which have been used in extremely large quantities, comes into serious problem due to their strong toxicity to men and cattle.

Hitherto, it is known that there are various kinds of organo-phosphorous compounds having either insecticidal activity or fungicidal activity. However, there has not been known any organo-phosphorous compound which has insecticidal activity as well as fungicidal activity.

The present inventors made repeated studies to find chemicals which maintain strong activity against insects and fungi without toxicity to mammals. As a result, the present inventors have found phosphorodithiolates of the above-mentioned formula are excellent agricultural insecticide and fungicide.

One object of the present invention is to provide a novel insecticidal and fungicidal use of the phosphorodithiolates of the above-mentioned formula. Other objects of the present invention will be clear from the following description.

In order to accomplish these objects, the present invention provides a method for controlling insects and fungi, which comprises contacting the insects and fungi with a phosphorodithiolate of the above-mentioned formula.

According to the present invention, the compounds of the present invention have such broad and excellent biological effects that they can control fungi simultaneously with injurious insects. In addition, they contain no such poisonous heavy metal as in the case of the organo-mercuric compounds and hence bring about a great advantage in handling.

The compounds of the present invention, which are represented by the formula as mentioned above, are obtained by reacting dithioate represented by the formula,

wherein A and R are as mentioned before; and M is an alkali metal atom or ammonium group, with halides represented by the formula,

B'Hal wherein B is as mentioned before; and Hal is a halogen atom.

Generally, the reaction of said dithioate with said halides is effected in the presence of organic solvents or water as solvents. When there are used as solvents those which are relatively high in polarity such as water, alcohols, ketones and acetonitrile, favorable results are obtained. However, there are some cases where the desired compounds can be obtained in high yields even in the absence of solvent.

The reaction conditions vary depending on the kind of starting materials employed. Generally, however, the reaction temperature is from room temperature to about C., and the reaction time is from 1 hour to about 20 hours. If the starting materials employed are difficult to react, reaction accelerator, e.g. iodide, may be added, whereby the reaction rates can be accelerated and the yields can be increased. After completion of the reaction, ordinary after-treatments are effected to obtain the desired compounds.

The phosphorodithiolates of the above-mentioned formula in which R isa C C alkyl; A is a phenylalkyl of the formula,

wherein D, X and n are as defined above; and B is an alkenyl group, an alkynyl group or a haloalkyl group; are novel compounds, and those in which R is a C C alkyl are preferably with respect to biological activity.

The dithiol phosphates obtained in the above manner may be practically used as such; but may further be purified according to column chromatography.

Typical examples of the compounds of the present invention are as exemplified below, but compounds which are in accord with the object of the present invention are, of course, not limited to these.

TABLE (1) O S CzH C2H50-P S CH2- (2) O S C2H H OAHQO-P S CH2- (3) O S(C4H9-SB0.)

I C:H OP

S CH2 (4) S-(CsHii-iSo.)

C2H OI S --CHz The preparation of the compounds used in the present invention will be illustrated below with reference to examples. But it is not need to say that the present invention is not limited to them.

EXAMPLE 1 To a solution comprising 12.6 g. of potassium O- ethyl-Sm-butyl phosphorodithioate and 50 ml. of water, 6.4 g. of benzyl chloride was added dropwise with stirring at 50C. The mixture was reacted at 60C. for 4 hours. Thereafter, the reaction liquid was extracted with toluene and was washed with a 5 percent aqueous sodium carbonate solution and then with water, and the toluene layer was dried with anhydrous glauber's salt. Subsequently, toluene was removed by distillation to obtain a light yellow oily substance which was O.ethyl-S-n-butyl-S-benayl phosphorodithiolate,

yield 89 percent. This substance was subjected to' column chromatography using active alumina. The refractive index of the thus treated substance was n 1.5510, and the elementary analysis values thereof were as follows:

Found Calculated EXAMPLE 2 To a solution comprising 15.0 g. of potassium O- ethyl-S-a-phenylethyl phosphorodithioate and 50 ml. of acetone, 6.7 g. of n-propylbromide was added dropwise with stirring at 50C., and the mixture was refluxed for 4 hours. The deposited potassium bromide was separated by filtration and acetone was removed by distillation. The residual oily substance was dissolved in toluene and was subjected to the same treatment as in Example 1 to obtain a light yellow oily substance which was O-ethyl-S-n-propyl S-a-phenylethyl phosphorodithiolate, yield 77 percent. This substance was subjected to column chromatography using active alumina. The refractive index of the thus'treated substance was n,, 1.5496, and the elementary analysis values thereof was as follows:

Found Calculated EXAMPLE 3 To a solution comprising 14.2 g. of sodium 1-ethyl-S- 2-phenylethyl phosphorodithioate and 50 ml. of water, 6.3 g. of benzyl chloride was added dropwise at 50C. over a period of about 1 hour, and the mixture was reacted with stirring at C. for 3 hours. Subsequently, the reaction liquid was subjected to the same treatments as in Example 1 to obtain a light yellow oily substance which was O-ethyI-SZ-phenylethyl-S-benzyl phosphorodithiolate, yield 92 percent. The refractive index of the substance was n 1.5834, and the elementary analysis values thereof were as follows:

Found Calculated EXAMPLE 4 To a solution comprising 14.9 g. of sodium O-nbutyl-S-benzyl phosphorodithioate and 50 ml. of water, 5.5 g. of ethyl bromide was added, and the mixture was reacted at 60C. for 8 hours. Subsequently, the same treatments as in Example 1 were effected to obtain a light yellow oily substance which was O-n-butyl-S- ethyl-S-benzyl phosphorodithiolate, yield 89 percent. The refractive index of this substance was n 1.5392, and the elementary analysis values thereof were as follows:

Found Calculated P(%) 10.10 10.17 S012) 21.37 21.07

According to Examples 1 to 4, the compounds shown in the Table 1 below were synthesized.

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The carriers to be used may be any of solids and liquids. As the solid carriers, there are used, for example, clay, talc, diatomaceous earth, bentonite, kaolin, acid clay and vermiculite. As the liquid carriers, there are employed, for example, water, alcohols, ketones, benzene, toluene, xylene, solvent naphtha, petroleum ether and purified kerosene. Further, as gas carriers there are used from gas, deodorized LPG, methyl chloride, vinyl chloride monomers, dimethyl ether, nitrogen and carbon dioxide. The abovementioned preparations can be used, either as such or after dilution with water, by such means as spraying or soil injection and can display their effects by so-called spraying to plant or soil application.

Further, the present compounds may be used in admixture with other chemicals to broaden the applicable scope thereof. For example, they may be used in ad mixture with organo-chlorine type fungicides such as pentachlorobenzyl alcohol and the like, organo-arsenic type fungicides such as iron methylarsonate and the. like, organo-sulfur type fungicides, or antibiotics. In addition thereto, they may be used in admixture with organo-chlorine type, organo-phosphorus type, pyrethroid type or carbamate type insecticides such as 7-1 ,2,3 ,4,5 ,6-hexachlorocyclohexane, l ,1 ,l-trichloro- 2,2-bis(p-chlorophenyl)ethane, 0,0-dimethyl-O-(pnitrophenyl) phosphorothioate, S-[l,2-bis(ethoxy-carbonyl)ethyl] 0,0-dimethyl phosphorodithioate, 0,0- dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate, O-ethyl O-p-nitrophenyl phenylphosphonothiorate, a-naphthyl N-methyl carbamate, 0,0-dimethyl-(p-nitro-m-methylphenyl) phosphorothioate, 3,4,5 ,6- tetrahydrophthalimidemethyl chrysanthemate and 3,4- dimethylphenyl N-methyl carbamate, and further with the above-mentioned fungicides. Further, they may be used in admixture with agricultural chemicals such as herbicides, e.g. 2,4-dichlorophenoxyacetic acid, 4- chloro-2-methylphenoxyacetic acid, 3,4- dichloropropionanilide, nematocides or miticides, or with fertilizers. A synergistic effects due to mixing can be expected depending on combinations with said chemicals.

The present invention will be illustrated in further detail below with reference to examples, but the kinds and mixing proportions of compounds and additives are not limited only to those shown in the examples but are variable within wide ranges. In Examples 69-96, the compounds are referred to number of the above mentioned typical compounds. All parts are based on weight.

EXAMPLE 69 DUST 3 Parts of compound (2) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3 percent of active ingredient. In application, the dust is dusted as such.

EXAMPLE 70 DUST 4 Parts of compound (73) and 96 parts of a clay-talc mixture are thoroughly pulverized and mixed together to obtain. a dust containing 4 percent of active ingredient. In application, the dust may be used either as such or in thorough admixture with a soil.

5 EXAMPLE 71 WETTABLE POWDER.

50 Parts of compound (7), 5 parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diactomaceous earth are thoroughly pulverized and mixed together to obtain a wettable powder containing 50 percent of active ingredient. In application, the powder is diluted with water and is then sprayed.

EXAMPLE 72 EMULSIFIABLE CONCENTRATE.

EXAMPLE 73 EMULSIFIABLE CONCENTRATE.

Parts of compound (68), 50 parts of toluene and 25 parts of the emulsifier Sorpol 2020 (registered trade name) (polyoxyethylene phenyl phenol polymer type) are mixed together to obtain an emulsifiable concen- -trate having an active ingredient concentration of 25 percent. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 74 OIL PREPARATION.

1 Part of compound (1) and 99 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of 1 percent. In application, the preparation is atomized or sprayed as much or is poured into a hole bored in a soil.

EXAMPLE 75 GRANULES.

5 Parts of compound (3), 93.5 parts of clay and 1.5 parts of Gohsenol (polyvinyl alcohol) (registered trade name) are thoroughly kneaded with water, and the mixture is granulated and is then dried to obtain granules containing 5 percent of active ingredient. In application, the preparation is applied as such.

EXAMPLE 76 DUST.

3 Parts of compound (40) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3 percent of active ingredient. In application, the dust is dusted as such.

EXAMPLE 77 DUST.

I 1.5 Parts of compound (22) and 98.5 parts of a claytalc mixture are thoroughly pulverized and mixed together to obtain a dust containing 1.5 percent of active ingredient. In application, the dust may be dusted as such or may be used in thorough admixture with a soil. 7

EXAMPLE 78 WETTABLE POWDER.

50 Parts of compound (27), 5 parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly pulverized and mixed together to obtain a wettable powder containing 50 percent of active ingredient.

EXAMPLE 79 EMULSIFIABLE CONCENTRATE.

50 Parts of compound (32), 20 parts of an emulsifier (polyoxyethylene alkylphenol ether type) and 30 parts of acetonitrile are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50 percent. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 80 EMULSIFIABLE CONCENTRATE.

40 Parts of compound (33), 20 parts of an emulsifier (polyoxyethylene alkylphenol ether type) and 40 parts of xylene are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 40 percent. In application, the concentrate is dilute with water and is sprayed. a

' EXAMPLE 8] OIL PREPARATION.

1 Part of compound (30) and 99 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of l percent. In application, the preparation is atomized or sprayed as such.

' EXAMPLE s2 GRANULES.

Parts of compound (5), 90 parts of silica powder, 4.95 parts of calcium lignosulfonate and 0.05 partof sodium alkylbenzenesulfonate are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 5 percent of active ingredient. In application, the preparation is sprinkled as such.

EXAMPLE 83 DUST.

3 Parts of compound (45) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3 percent of active ingredient. In application, the dust is dusted as such.

EXAMPLE 84 DUST.

2 Parts of compound (50) and 98 parts of a clay-talc mixture are thoroughly pulverized and mixed together to obtain a dust containing 4 percent of active ingredient. In application, the dust may be dusted as such or may be used in thorough admixture with a soil.

EXAMPLE 85 WETTABLE POWDER.

50 Parts of .compound (47), 5 parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly pulverized and mixed together to obtain a wettable powder containing 50 percent of active ingredient. In application, the powder is diluted with water and is sprayed.

EXAMPLE 86 EMULSIFIABLE CONCENTRATE.

50 Parts of compound (46), 35 parts of xylene and parts of an emulsifier (polyoxyethylene alkylphenol ether type) are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50 percent. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 87 EMULSIFIABLE CONCENTRATE.

40 Parts of compound (49), 40 parts of acetonitrile and parts of an emulsifier (polyoxyethylene alkylphenol ether type) are mixed together to obtain an emulsifiable concentrate having an. active ingredient concentration of 40 percent. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 88 OIL PREPARATION.

0.5 Part of compound (48) and 99.5 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of 0.5 percent. In application, the preparation is atomized or sprayed as such.

EXAMPLE 89 GRANULES.

3 Parts of compound (57') and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3 percent of active ingredient. In application, the dust is dusted as such.

EXAMPLE 91 WETTABLE POWDER.

50 Parts of compound (59), 5 parts of wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly pulverized and mixed together to obtain a wettable powder containing 50 percent of active ingredient. In application, the powder is diluted with water and sprayed.

EXAMPLE 92 EMULSIFIABLE CONCENTRATE.

50 Parts of compound (53), 35 parts of xylene and 15 parts of an emulsifier (polyoxyethylene alkylphenol ether type) are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50 percent. In application, the concentrate is diluted with water and is then sprayed.

EXAMPLE 93 OIL PREPARATION.

0.5 Part of compound (55 and 99.5 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of 0.5 percent. In application, the preparation is atomized or sprayed as such.

EXAMPLE 94 GRANULES.

5 Parts of compound (61 parts of silica powder, 4.95 parts of calcium lignosulfonate and 0.05 part of sodium alkylbenzensulfonate are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 5 percent of active ingredient, In application, the preparation is sprinkled as such.

EXAMPLE 95 EMULSIFIABLE CONCENTRATE.

50 Parts of compound (69), 30 parts of an emulsifier (polyoxyethylene alkylphenol ether type) and 20 parts of xylene are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50 percent. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 96 GRANULES.

3 Parts of compound (72), 95 parts of clay and 2 parts of Gohsenol (polyvinyl alcohol) (trade name for a product of Nippon Gosei Chemical Co., Ltd.) are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 3 percent of active ingredient. In application, the preparation is sprinkled as such.

In order to substantiate the excellent preventive and exterminative effects of the present compounds, typical test results will be shown below. In Tables of the following Test Examples, the compounds are referred to by the numbers of the above-mentioned typical compounds.

TEST EXAMPLE 1 Test of Control of Rice Blast:

In a 9 cm in diameter flower pot, a rice plant (variety: Waseasahi") was cultivated to the 34 leaves stage. To the rice plant, each 100 mg. per pot of the present composition in the form of dusts were individually dusted by use of a bell jar duster. After 1 day, the rice plant was sprayed and inoculated with a sporesuspension of rice blast fungi (Pyricularia oryzae). 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compositions. The results are as shown in Table 2.

TABLE 2 Active ingredient Preventive Compound concentration (96) value 3 I 3 97.3 (7) 3 100 (9) 3 I00 (10) 3 98.9 (13) 3 I00 (18) 3 96.8 (20) 3 95.7 Phenylmercuric acetate dust 0.42 98.1

t (CI-l sh? OCH, 3 48.9

C Has 0 f P CHBO S'CH2CN 3 57.3

Non-treatment TEST EXAMPLE 2 Test of Curative Effects on Rice Blast:

In a 9 cm in diameter flower pot, a rice plant (variety: Waseasahi) was cultivated to the 3 leaves stage. The rice plant was sprayed and inoculated with a spore-suspension of rice blast fungi (Pyricularia oryzae). After I day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 7 ml. per pot. 3 Days thereafter, the number of spot generated was counted to investigate the fungicidal effects of individual compounds. The results are as shown in Table 3.

noonnsnl o -Q Non-treatment 0 In Tables 2 and 3, the preventive and curative values indicate numeral values calculated according to the following equation:

Number of spots Number of spots -in treated in non-treated Preventive 77 arca area $33? 0) Number of spgltzain non-treated X TEST EXAMPLE 3 Test on the Control of Rice Sheath Blight:

A rice plant (variety: Kinnanpu") was cultivated in a porcelain pot. When the rice plant had grown to a height of about 50 cm, disk inoculum (5 mm in diameter) of the mycelium of Pellicularia sasakii was inoculated onto the leaf sheaths of the rice plant. After 1 day, the present compound in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 10 ml. per pot. 5 Days thereafter, the number of affected leaf sheaths was counted to obtain the results as shown in Table 4.

TABLE 4 Active ingredient Ratio of concentration affected leaf Compound (p.p.m.) sheaths (5%) (6) 1,000 31.9

r ms 0 vino sc1w 1.000 80.1

Non-treatment 88.5

TEST EXAMPLE 4 A rice seedling (variety: Waseasahi) at the 3-4 leaves stage, which had elapsed 30 days after sowing, was immersed for 1 minute in an emulsion prepared by individually diluting with water to a given concentration the present compounds in the form of emulsifiable concentrates. After air-drying, the rice seedling was placed in a large size test tube. Subsequently, 30 adults of small brown planthopper (Delphacodes striatellus Fallen) were liberated in said test tube. After 24 hours, the number of killed insects was calculated, and the values of LC were calculated from the mortality. The results are as shown in Table 5.

TABLE 5 Compound LC (times) (2) 40.000 25,000

cmo \S-CH2 No. 200

TEST EXAMPLE 5 A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing in a 9 cm. flower pot, was parasitized with large number of towspotted red spider mite (Tetranychus telarius Linne). The present compounds in the form of wettable powders were individually diluted with water to agiven concentration, and the solution was sprayed in a proportion of ml. per pot to the mottled kidney bean plant on a turn table. After 48 hours, the alive and dead of the red spider mite were observed to calculate the mortality thereof. The results are as shown in Table 6. I

TABLE 6 Active ingredient Compound concentration (times) Mortalit TEST EXAMPLE 6 in a 25 cm. in diameter flower pot, a mottled kidney bean plant was grown to the 3-4 leaves stage. The plant was parasitized with 5 tow spotted red spider mite (Tetranychus telarius LINNE) per leaf. After 3 days,

treated area area '24 7 TEST EXAMPLE 7 Test of Preventive Effects on Rice Blast: ln a 9 cm. flower pot, a rice plant (variety:

5 Waseasahi") was cultivated to the 3-4 leaves stage. To the rice plant, the present compounds in the form of dusts were individually dusted in a proportion of 100 mg. per pot by use of a bell jar duster. After 1 day, the rice plant was sprayed and inoculated with a spore- 10 suspension of rice blast fungi (Pyricularia oryzae). 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. The results are as shown in Table 8.

TABLE 8 Active ingredient Preventive Compound concentration value (24) 3.0 100 Phenylmercuric acetate 0.42 95.4

Non-treatment 0 l 2 TEST EXAMPLE 8 Test of Curative Effects on Rice Blast:

A rice plant (variety: Waseasahi), which had been cultivated to the 3 leaves stage in a 9 cm. flower pot, was sprayed and inoculated with a spore-suspension of rice blast fungi (Pyricularia ory zae). After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed in a, proportion of 7 ml. per pot. 3 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. The results are as shown in Table 9.

Non-treatment 0 TEST EXAMPLE 9 Test on the Control of Rice Sheath Blight:

A rice plant (variety: Kinnanpu") was cultivated in a porcelain pot. When the rice plant had grown to a height of about 50 cm., a dick inoculum mm. in diameter) of the mycelium of Pellicularia sasakii was innoculated onto the leaf sheaths of the rice plant. After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of ml. per pot. 5 Days thereafter, the number of affected leaf sheaths was counted to obtain the results as shown in Table 10. 9

TABLE 10 Active ingredient Ratio of affected concentration leaf sheath Compound (ppm) (5%) 1000 8.7 (27) 1000 13.2 (32) 1000 11.1 (41) 1000 33.5 Non-treatment 100 TEST EXAMPLE I0 (I) Test of Effects on Smaller Brown Planthoppers:

A rice seedling which had elapsed 35 days after sowing was immersed for 1 minute in each of given concentration solution of the present compounds in the form of emulsifiable concentrates. After air-drying, the rice seedling was placed in a large size test tube. Into the test tube, adults of smaller brown planthopper (Delphacodes striatellus Fallen) were liberated. After 24 hours, the mortality of insects at given concentrations were measured, and the values of I..C were calculated from said mortality. The results are as shown in Table 11.

(ll) Test of Effects on Tow-Spotted Red Spider Mite (Tetranychus telarius LINNE):

A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of red spider adults. The plant was immersed for 1 minute in each of given concentration liquids of the present compounds in the form of wettable powders. After 48 hours, and the values of LC were calculated from said mortality. The results are as shown in Table l 1.

TABLE 1 1 LC, (times) Compound Planthoppers Spider mites (23) 4,000 35,000 (24) 4,000 500,000 (25) 60,000 200,000 (26) 100,000 200,000 (27) 60,000 350,000 (28) 10,000 210.000 (31) 180.000 200.000 (34) 100,000 340,000 (36) 230,000 150,000 (37) 1 10,000 170,000 (38) 500,000 250,000 (39) 1 10,000 300,000 (4l 300,000 430,000 (42) 520,000 380.000

l (n-(nmsM 200 250 TEST EXAMPLE 11 Test of Preventive Effects on Rice Blast:

A rice plant (variety: Waseasahi") was cultivated in a 9 cm. flower pot to the 3-4 leaves stage. To the rice plant, the present compounds in the form of dusts were individually dusted by use of a bell jar duster in a proportion of mg. per pot. After 1 day, the rice plant was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds, whereby each of the present compounds showed a preventive effect comparable to that of the control phenylmercuric acetate, as set forth in Table 12.

TABLE 12 Active ingredient Preventive Compound concentration (96) value (43) 2.0 100 (45) 2.0 98.6 (47) 2.0 98.7 (48) 2.0 84.3 (49) 2.0 85.9 (50) 2.0 83.2 (51) 2.0 94.6 (52) 2.0 95.7 Control phenylmercuric acetate 0.42 93.5 Control O-ethyl-S-p-tolyl S-p-chlorobenzyl trithiophosphate (Compound disclosed in 2.0 49.1 Japanese Patent Publication 15,600/66) Non-treatment 1 i 0 TEST EXAMPLE 12 Test of Curative Effects on Rice Blast.

A rice plant (variety: Waseasahi"), which had been cultivated in a 9 cm. flower pot to the 3 leaves stage, was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 7 ml. per pot. 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds, whereby the present compounds showed far more excellent curative effects than those of commercially available mercury preparation, organophosphorus fungicide and the like, as set forth in Table 13.

TABLE 13 Active ingredient 27 i? (CH,S),P CH 100 5.6

O n-o,Hs 1i o- 0 7.1

Non-treatment 0 TEST EXAMPLE 13 Test of the Control of Rice Sheath Blight:

A rice plant (variety: Kinnampu") was cultivated in a porcelain pot. When the plant had grown to a height of about 60 cm., the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the plant in a proportion of 10 ml. per pot. After 2 hours, a disk inoculum (5 mm. in diameter) of the mycelium of Pellicularia sasakii was inoculated on the leaf sheaths of the plant. 5 Days thereafter, the number of affected leaf sheaths was counted to obtain the results as shown in Table 14.

TABLE 14 Active ingredient Ratio of concentration affected leaf Compound (p.p.m.) sheaths (43) 1000 16.8 (46) 1000 43.2 (47) 1000 14.3 (48) 1000 47.9 Non-treatment 100 TEST EXAMPLE 14 TABLE 15 Compounds LC (times) (44) 4,000,000 (46) 1,000,000 1,000,000 (48) 1,000,000 (49) 1,000,000 (52) 600,000 Dimethoate (control) 500,000

if ((n)C,l-1 S) P 0 CH, 60,000

TEST EXAMPLE 15 Well water was charged in a 500 cc. beaker. Into the beaker, full grown larvae of northern house mosquitoes 55 were liberated, and then the present compounds in the form of granules were individually charged. After 24 hours, the alive and dead of the mosquito larvae were observed to calculate the mortality thereof. The results are as shown in Table 16.

TABLE 16 Compound LC (ppm) (44) 0.13

TEST EXAMPLE 16 Test of Curative Effects on Rice Blast:

A rice plant (variety: Waseasahi), which had been cultivated in a 9 cm. flower pot to the 3 leaves stage, was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the plant in a proportion of 7 ml. per pot. 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. The results are as set forth in Table 17, and the present compounds showed markedly excellent curative effects as compared with control compounds.

TABLE 17 Active ingredient Number of TEST EXAMPLE 17 Test of Preventive Effects on Rice Blast:

To a rice plant (variety: Waseasahi"), which had been cultivated in a 9 cm. flower pot to the 3-4 leaves stage, the present compounds in the form of dusts were dusted in a proportion of mg. per pot by use of a bell jar duster. After 1 day, the plant was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. 5 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. The results are as set forth in Table 18, and the present compounds were comparable in preventive effect to the control phenylmercuric acetate.

TEST EXAMPLE 18 Test Of Effects On Tow-Spotted Spide Mite:

A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing was parasitized with a large number of adults of Tetranychus telarius LINNE. The leaves of said plant parasitized with said spider mites were immersed for 1 minute in each of aqueous solutions of the present compounds in the form of wettable powders. After 48 hours, the alive and dead of the red spider were observed to calculated the mortality thereof. The results are as shown in Table 19.

TABLE 19 Compound LC (times) (55) 510,000 (57) 260,000 (58) 3,000,000 (59) 900,000 Control Dimethoate (Commercially available compound) 250,000 Control -ethyl-S,S-diphenyl phosphorodithiolate (Known compound) 10,000

TEST EXAMPLE 19 Test of Insecticidal Effects on Adzuki Bean Weevil:

About 30 adults of Callosobruchus chinensis Linne were liberated in a stryolmade tube of 2 cm. in diameter and 7 cm. in length. Both ends of the tube were corked with polyethylene film-covered corks. Into the tube, aqueous emulsion of the present compounds in the form of emulsifiable concentrates were individually charged, and the insects were immersed therein for 1 minute. Subsequently, the insects were taken out on a filter paper and were then transferred to a dish for observation. After 24 hours, the alive and dead of the insects were observed to calculate the mrtality thereof.

The results are as shown in Table 20.

TABLE 20 Compound LC (times) (53) 34,000 (57) 66,000 (58) 118,000 (59) 1 1,000 (62) 30,000 Control 0-ethyl-S,S-dip henylphosphorodithiolate (Known compound) 250 Control Dimethoate (Commercially available compound) 5,000 Control Sumithion (Commercially available compound) 50,000

(ills o TEST EXAMPLE 20 Test of Preventive Effects on Rice Blast:

A rice plant (variety: Waseasahi) was cultivated in a 9 cm. flower pot to the 3 leaves stage. To the rice plant, given concentration liquids of test compounds were individually sprayed in a proportion of 7 ml. per pot. After 2 hours, the rice plant was sprayed and inoculated with a spore-suspension of Pyncularia oryzae. 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of the test compounds. The results are as shown in Table 21.

Control 200 TABLE 21 Active ingredient concentration Preventive Compound (p.p.m.) value (63) 98.2 500 100 Phenylmercuric acetate 30 97.6 Non-treatment 0 TEST EXAMPLE 21 Test of Curative Effects on Rice Blast:

A rice plant (variety: Waseasahi) was cultivated in a 9 cm. flower pot to the 3 leaves stage. The rice plant was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. After 1 day, given concentration liquids of test compounds were individually sprayed to the plant in a proportion of 7 ml. per pot. 3 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of the compounds. The results are as shown in Table 22.

TABLE 22 Active ingredient concentration Curative Compound (p.p.m.) value 63) 500 97.8 500 96.8 Phenylmercuric acetate 30 50.4 Non-treatment 0 TEST EXAMPLE 22 In a porcelain Wagner pot, a pea plant was grown to a height of 20 cm. The plant was parasitized with a large number of adults of Tetranychus lelarius Linne. Subsequently, 0.02 percent solution of the emulsifiable concentrate of Example shown before was applied to the root portion of said plant in a proportion of 20 cc. per pot. When observed after 10 days, all the red spider had been killed.

TEST EXAMPLE 23 Test of Preventive Effects on Rice Blast:

The procedure of TestExample 21 was repeated except that the following compounds were used instead of the compounds 63) and (64). The results are shown in Table 23.

TEST EXAMPLE 24 Effect of Controlling Powdery Mildew of Cucurbitaceous Plants:

Pumpkin plants (variety: l-leiankogiku) were cultivated in the flower pots of 12 cm. in diameter. When the plant had grown to the 3-4 leaves stage, they were individually sprayed with 7 ml/pot of each of given concentration solutions of test chemicals in the form of wettable powders. One day after, the pumpkin seedlings were sprayed to inoculate with a sporesuspension of cucurbitaceous plant powdery mildew fungi (Sphaerotheca fuliginea). 10 Days thereafter, the state of disease of 4 leaves at the upper portion of each plant was observed and the diseased degree of the plant was calculated from the area of diseased spots generated.

In each treatment, 7 pots were tested to obtain the result shown in Table 24 below. As seen in the table, the present compounds showed markedly excellent controlling effects as compared with that of the conventional fungicide, sulfur.

TABLE 24 Active ingredient concentration Degree of Compound (p.p.m.) damage (66) 1,000 8.6 (68) 1,000 15.6 1,000 10.3 (72) 1,000 9.4 (75) 1,000 17.4 (76) 1,000 19.5 (78) 1,000 16.3 1.000 9.7 Sulfur 2,500 10.2 Non-treatment 67.8 Commercially available fungicide for controlling the powdery mildew.

TEST EXAMPLE 25 The procedure of Test Example 14 was repeated substituting the following compounds for the compounds used in said Example. The results are shown in Table 25.

TABLE 25 Compound LC (times) (66) 430,000 (67) 1,300,000 (68) 9,600,000 (69) 13,000,000 8,600,000 12,000,000 8.000.000 (73) 46,000,000 6,600,000 12,000,000 1,200,000 200,000 380.000 (80) 200,000

TEST EXAMPLE 26 The procedure of Test Example was repeated substituting the following compounds for the compounds 5 used in said Example. The results are shown in Table TABLE 26 c 1 LC 10 l 0.03 3 p m TEST EXAMPLE 27 The procedure of Test Example 19 was repeated substituting the following compounds for the compounds used in said Example. The results are shown in Table 27.

TABLE 27 Compound LC (times) (68) 235,000 (69) 215,000 70) 130,000 (71) 330,000 (72) 300,000 (73) 240,000 (74) 130,000 (75) 215,000 128,000 (78) 71,000

What we claim is:

1. A method for controlling, insects and fungi, which comprises contacting, the insects and fungi with an insecticidally and fungicidally effective amount of a phosphorodithiolate of the formula wherein R is C C alkyl, A is phenylalkyl of the formula \h/ wherein D is C C alkylene, X is hydrogen, chlorine, C C alkyl or nitro and n is an integer of l to 5, and B is C C,,, alkyl, C C alkenyl, propargyl, chlorinated C C alkyl, cyclohexyl or a phenylalkyl group of the formula -6. An insecticidal and fungicidal composition consisting of an insecticidally and fungicidally effective amount of a phosphorodithiolate as defined in claim 1 and an agriculturally acceptable carrier.

# i i i i 

2. The method according to claim 1 wherein the phosphorodithiolate is O-ethyl-S-n-butyl-S-benzylphosphorodithiolate, O-n-butyl-S-ethyl-S-benzylphosphorodithiolate or O-ethyl-S-sec-butyl-S-benzylphosphorodithiolate.
 3. A method for protecting plants from insects and fungi, which comprises applying to said plants an insecticidally and fungicidally effective amount of a phosphorodithiolate as defined in claim
 1. 4. The method according to claim 1, wherein the alkyl of R is ethyl, straight or branched propyl, straight or branched butyl or straight or branched pentyl.
 5. The method according to claim 1, wherein R is ethyl or n-butyl; A is phenethyl or phenpropyl and B is benzyl or 3,4-dichlorobenzyl.
 6. An insecticidal and fungicidal composition consisting of an insecticidally and fungicidally effective amount of a phosphorodithiolate as defined in claim 1 and an agriculturally acceptable carrier. 